CN102083623A - Multilayer articles and methods for making multilayer articles - Google Patents

Multilayer articles and methods for making multilayer articles Download PDF

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Publication number
CN102083623A
CN102083623A CN2009801032172A CN200980103217A CN102083623A CN 102083623 A CN102083623 A CN 102083623A CN 2009801032172 A CN2009801032172 A CN 2009801032172A CN 200980103217 A CN200980103217 A CN 200980103217A CN 102083623 A CN102083623 A CN 102083623A
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sheet material
cycloaliphatic polyesters
present cycloaliphatic
basal layer
copolymer
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CN102083623B (en
Inventor
桑迪普·特里帕西
施里瓦斯·查克拉瓦蒂
萨普纳·K·布莱克本
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SABIC Global Technologies BV
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SABIC Innovative Plastics IP BV
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/536—Hardness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/54—Yield strength; Tensile strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/582—Tearability
    • B32B2307/5825—Tear resistant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/738—Thermoformability
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/75—Printability
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/762—Self-repairing, self-healing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2451/00—Decorative or ornamental articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2509/00—Household appliances
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • Y10T428/2495—Thickness [relative or absolute]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/269—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension including synthetic resin or polymer layer or component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31—Surface property or characteristic of web, sheet or block
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31507—Of polycarbonate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31786—Of polyester [e.g., alkyd, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31786—Of polyester [e.g., alkyd, etc.]
    • Y10T428/31797—Next to addition polymer from unsaturated monomers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31935—Ester, halide or nitrile of addition polymer

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)

Abstract

The present application relates to a sheet comprising a cap layer comprising an acrylic polymer; and a base layer, wherein the sheet is thermof ormable. The base layer comprises a cycloaliphatic polyester copolymer and optionally an aromatic polycarbonate. The cycloaliphatic polyester copolymer comprises greater than 10 wt% cycloaliphatic diol or acid or combination thereof, based upon a total weight of the cycloaliphatic polyester copolymer.

Description

Multi-layer product and the method for preparing multi-layer product
Background
The thermoplastic film of in-mold decoration is obtaining to accept described various application examples such as domestic consumer electronics, articles for use and the covering of printing widely in various application.The combination of the various character of these application needs, for example transparent, impressionability, thermal formability, and hardness, and scratch resistance, chemical resistance and resistance to impact.Many selected materials all can not obtain these combinations.The most common solution be with the functional form coating as on the cap rock paint thermoplastic film, wherein said coating is given surface nature, simultaneously Ranvier's membrane provides big mechanical integrity.But though coating is improved scratch resistance, it can damage the thermal formability of film, and this has seriously limited the advantageous application of this film.One of the most difficult challenge is the balance that still exists between scratch resistance and the thermal formability.
Therefore, prior art still need can be easily the multi-layer sheet by extrusion molding for example, and this sheet material provides the expectation combination of various character, described various character comprise thermal formability and scratch resistance.
Summary of the invention
The present invention generally relates to thermoformable material, prepares the method and the goods prepared therefrom of thermoformable sheet material.In one embodiment, described sheet material comprises: the cap rock that contains acrylic polymer; And basal layer, wherein said sheet material is thermoformable.Described basal layer comprises present cycloaliphatic polyesters copolymer and optional aromatic polycarbonate.Described present cycloaliphatic polyesters copolymer can comprise greater than the alicyclic diol of 10wt% or acid or its combination, based on the gross weight of present cycloaliphatic polyesters copolymer.
In one embodiment, the method for preparing goods can comprise: make acrylic polymer fusion in extruder; In extruder, form present cycloaliphatic polyesters copolymer and the described acrylic polymer of coextrusion and the described present cycloaliphatic polyesters copolymer of fusion, thereby form sheet material.Described present cycloaliphatic polyesters copolymer can comprise that content is the present cycloaliphatic polyesters greater than 10wt%, based on the gross weight of present cycloaliphatic polyesters copolymer.Described present cycloaliphatic polyesters copolymer can form basal layer, and described acrylic polymer forms cap rock on described basal layer.
By with reference to the following detailed description of various features of the present disclosure be included in wherein embodiment, can more easily understand the disclosure.
Description of drawings
With reference now to accompanying drawing,, this accompanying drawing only is illustrative, is not limitation of the present invention.
Fig. 1 is the cross-sectional illustration by the scraping that type load (profile load) generation is arranged.
Fig. 2 is the schematic diagram of exemplary coextrusion system.
The specific embodiment
Multi-layer product comprises cap rock and basal layer.Described cap rock can be based on those (for example, poly-(methyl methacrylate (" PMMA ")), and basal layer can be the combination of present cycloaliphatic polyesters copolymer and optional aromatic polycarbonate of for example poly-(methyl) alkyl acrylate of acrylic polymer.Described cap rock and basal layer coextrusion can be formed multi-layer sheet.
The hardness of this goods, scratch resistance, mechanical strength and thermal formability should make these goods satisfy the expectation combination of various character, described various character is the transparency for example, impressionability, thermal formability, and hardness, and scratch resistance, chemical resistance and resistance to impact.In addition, described basal layer is bonded to described cap rock, and without any need for adhesive or adhesive layer, and moulds in described cap rock and institute substantial rheological characteristic coupling is provided between the basal layer, improves the processability of complexes membrane thus.
In one embodiment, described sheet material comprises: the cap rock that contains acrylic polymer; And basal layer, wherein said sheet material is thermoformable.Described basal layer comprises present cycloaliphatic polyesters copolymer and optional aromatic polycarbonate.Described present cycloaliphatic polyesters copolymer can comprise greater than the alicyclic diol of 10wt% or acid or its combination, based on the gross weight of present cycloaliphatic polyesters copolymer.Described cap rock can be 1% to 50% of gross thickness, and described gross thickness can be 5mil to 500mil.Described basal layer can comprise the blend of the Merlon of 25wt% to 100wt% present cycloaliphatic polyesters and surplus, perhaps, especially, the blend of the Merlon of 50wt% to 90wt% present cycloaliphatic polyesters and surplus.The pencil hardness of described sheet material can be greater than HB.Pencil hardness also can comprise greater than the sheet material of HB: causes intensity (tear initiation strength) and/or spreads intensity more than or equal to tearing of 120N/mm greater than tearing of 5N/mm, and/or greater than the tensile strength of 40MPa.Acrylic polymer can be poly-(methyl) alkyl acrylate, perhaps especially, poly-(methyl) methyl acrylate.Described basal layer can comprise the PCCD of 20wt% to 90wt%, the aromatic polycarbonate of surplus.
In one embodiment, the method for preparing goods can comprise: make acrylic polymer fusion in extruder, in extruder, form present cycloaliphatic polyesters copolymer and the described acrylic polymer of coextrusion and the described present cycloaliphatic polyesters copolymer of fusion, thereby form sheet material.Described present cycloaliphatic polyesters copolymer can comprise that content is the present cycloaliphatic polyesters greater than 10wt%, based on the gross weight of present cycloaliphatic polyesters copolymer.Described present cycloaliphatic polyesters copolymer can form basal layer, and described acrylic polymer forms cap rock on described basal layer.Can make described sheet heat forming.
Described present cycloaliphatic polyesters has following formula:
R wherein 13And R 14Be aromatics independently of one another with 2 to 20 carbon atoms, aliphatic or cycloalkane, condition is R 13And R 14In at least one be alicyclic group.Described present cycloaliphatic polyesters is a condensation product, wherein R 13Be the residue of glycol or its chemical equivalence thing, R 14It is the residue of diacid or its chemical equivalence thing.In one embodiment, R 13And R 14It all is the group that contains cycloalkyl.These polyester contain alicyclic diacid and/or the alicyclic diol component of 50mol% at least usually, if residue exists, then are aromatic diacid and/or linear aliphatic family glycol.
In one embodiment, R 13And R 14Be cycloalkyl, it is independently selected from following construction unit:
Figure BPA00001186546600032
In concrete embodiment, described glycol is 1,4-cyclohexanedimethanol or its chemical equivalence thing.Can use 1, any of the cis of 4-cyclohexanedimethanol or transisomer or two kinds.The chemical equivalence thing of this glycol comprises ester, for example C 1-4Dialkyl, diaryl ester, etc.The concrete limiting examples of diacid comprises the decahydronaphthalenes dicarboxylic acids, norbornene dicarboxylic acids, double-octane dicarboxylic acids, 1,4-cyclohexane dicarboxylic acid or its chemical equivalence thing.The most particularly, diacid comprises anti-form-1,4-cyclohexane dicarboxylic acid or its chemical equivalence thing.The chemical equivalence thing of these diacid comprises C 1-4Dialkyl, diaryl ester, acid anhydrides, salt, acyl chlorides, acylbromide, etc.In one embodiment, described chemical equivalence thing comprises the dialkyl of alicyclic diacid and dimethyl esters that the most particularly should acid, for example 1, and 4-cyclohexane-dimethyl dicarboxylate.
The unit of other type can be present in the described present cycloaliphatic polyesters copolymer, comprises being derived from aromatic dicarboxylic acid component and non--alicyclic diol, or the unit of the reaction of its chemical equivalence thing.Exemplary aromatic dicarboxylic acid comprises M-phthalic acid, terephthalic acid (TPA), and 1,2-two (to carboxyl phenyl) ethane, 4,4 '-the dicarboxyl diphenyl ether, 4,4 '-diphenic acid, 1,4-, 1,5-, perhaps 2,6-naphthalene dicarboxylic acids and comprise the combination of at least a aforementioned acid.Concrete dicarboxylic acids is a terephthalic acid (TPA), M-phthalic acid and comprise the combination of two kinds of aforementioned acid.Described non--alicyclic diol can be C 1-4Aklylene glycol, ethylene glycol for example, propane diols, 1, the 4-butanediol, etc., and the combination that comprises at least a aforementioned glycol.
Described present cycloaliphatic polyesters copolymer more specifically comprises the alicyclic residue of 50mol% at least, the alicyclic residue of 70mol% at least more specifically, and remaining is aromatic acid or C 1-4The aklylene glycol residue.Concrete present cycloaliphatic polyesters is poly-(cyclohexane-1,4-Dimethylenecyclohexacompound-1,4-dicarboxylic ester), is also referred to as poly-(1,4-cyclohexane-dimethanol-1,4-dicarboxylic ester) (PCCD).Another concrete ester is that poly-(1,4-cyclohexylidene dimethylene copolymerization-ethylidene terephthalate) (PCTG), wherein the ester group greater than 50mol% is derived from 1, the 4-cyclohexanedimethanol; With poly-(ethylidene-copolymerization-1,4-cyclohexylidene dimethylene terephthalate) (PETG), wherein greater than the ester group body source of 50mol% from ethylidene.Also expect be used for the application be any above-mentioned polyester and a small amount of for example unit that is derived from aliphatic acid and/or aliphatic polyol of 0.5 to 5wt% forms copolyesters.Described aliphatic polyol comprises glycol, for example poly-(ethylene glycol) or poly-(butanediol).
Aromatic polycarbonate has following formula:
Figure BPA00001186546600041
R wherein 1At least 60% of group sum is the aromatics organic group, and all the other are aliphatic, alicyclic or aromatic group.The used term " Merlon " of the application comprises Copolycarbonate, promptly comprises two kinds or more kinds of different R 1The copolymer of group.In one embodiment, each R 1Be derived from the bisphenol compound of following formula:
Figure BPA00001186546600042
R wherein aAnd R bRepresent halogen atom or monovalence alkyl separately, and can be identical or different; P and q are 0～4 integer independently of one another, X aOne of group that expression is following:
Figure BPA00001186546600043
R wherein cAnd R dBe hydrogen atom independently of one another, perhaps monovalence linearity or cyclic hydrocarbon group, R eBe bivalent hydrocarbon radical.
The instantiation of bisphenol compound comprises 1, two (4-hydroxy phenyl) methane of 1-, 1, two (4-hydroxy phenyl) ethane of 1-, 2, two (4-hydroxy phenyl) propane (hereinafter being called " bisphenol-A " or " BPA ") of 2-, 2, two (4-hydroxy phenyl) butane of 2-, 2, two (4-hydroxy phenyl) octanes of 2-, 1, two (4-hydroxy phenyl) propane of 1-, 1, two (4-hydroxy phenyl) normal butanes of 1-, 2, two (4-hydroxyl-1-aminomethyl phenyl) propane of 2-, 1, two (4-hydroxyl-tert-butyl-phenyl) propane of 1-, 3, two (4-hydroxy phenyl) benzo [C] pyrrolones of 3-, 2-phenyl-3, two (4-hydroxy phenyl) benzo [C] pyrrolones (PPPBP) and 1 of 3-, two (the 4-hydroxy-3-methyl phenyl) cyclohexanes (DMBPC) of 1-.Also can use the combination that comprises at least a aforementioned bisphenol compound.For example, can use copolymer, comprise being derived from bisphenol-A and 1, the mixture of the unit of two (the 4-hydroxy-3-methyl phenyl) cyclohexanes of 1-.
In concrete embodiment, Merlon is the linear homopolymer that is derived from bisphenol-A, and wherein p and q respectively do for oneself 0, Y 1Be isopropylidene.
The relative quantity of present cycloaliphatic polyesters component and aromatic polycarbonate component changes along with concrete application.In one embodiment, the amount of polyester components is greater than 10wt%, and for example, 25wt% to 100wt%, residue are aromatic polycarbonate.In another embodiment, the amount of present cycloaliphatic polyesters is 50wt% to 90wt%, and residue is an aromatic polycarbonate.Described base layer composition can with
Figure BPA00001186546600051
Be purchased Plastics from GE.
Described cap rock can for example gather those (for example, poly-(methyl methacrylate (" PMMA ")) of (methyl) alkyl acrylate based on acrylic polymer.This layer can comprise the acrylic polymer more than or equal to 50wt%, perhaps particularly, and more than or equal to the acrylic polymer of about 70wt%, perhaps more specifically, more than or equal to the acrylic polymer of about 90wt%, based on the gross weight of cap rock.Residue can be and causes cap rock to have any other polymer more than or equal to 80% light transmittance when with the acrylic polymer blend, described light transmittance is measured according to ASTM D1003-00 method A, for example, use is from the HAZE-GUARD DUAL of BYK-Gardner, use integrating sphere (0 °/scattering geometry structure (diffuse geometry)) to measure, wherein spectral response meets the CIE standard spectrum value under standard lamp D65.
Except above-mentioned substance, described basal layer and/or cap rock can comprise various additives independently, thereby condition is to select described additive to make significantly not influence for example thermal formability of the desirable properties of this layer nocuously, scratch resistance, etc.Can use the combination of additive.Can in the process of the component of the composition that is mixed for forming each layer, mix these additives in the suitable time.Possible additive comprises antioxidant, fire retardant, dripping inhibitor, dyestuff, pigment, colouring agent, stabilizing agent (for example, heat stabilizer, ultra-violet stabilizer, etc.), small-particle mineral (clay for example, mica, and/or talcum), antistatic agent, plasticizer, lubricant, releasing agent, brightening agent, reinforcer (for example, glass) and comprise the combination of at least a aforementioned substances.The amount of additive can be and is less than or equal to about 20wt%, and perhaps about particularly 0.1wt% is to the additive of about 10wt%, and perhaps more specifically, about 0.5wt% is to the additive of about 5wt%, based on the gross weight of the layer that comprises described additive.
Cap rock of the present invention and basal layer form by coextrusion.For example, this layered composite can be suitably by using the continuous calendering coextrusion method that illustrates to meaning shown in Fig. 2 to form.In the method, single screw extrusion machine 1 and 2 resin melt with each layer (that is, top layer, the second layer and any other polymeric layer) are fed in the feed zone 3.Die head 4 forms the polymeric web of fusion, and it is fed to 3 rollers-calender 5.Usually, described calender comprises 2 to 4 reverse rotation cylinder rollers, and wherein each the free metal of each roller (for example, steel) or the metal of rubber-coated are made.Can be as required with each roller heating or cooling.Can be continuously extruded between stack by the fusion net that die head forms.Determine the thickness of each layer so as to the space between the roller of pulling out this net or " roll gap ".Layered composite also can be formed by the independent preformed film corresponding to polymeric layer, then for example uses the roller of heating and optional adhesive bond layer that described independent preformed film is laminated to together.
But thereby each layer of coextrusion forms the thickness of various cap rocks and basal layer than (that is, depth of cover is divided by base layer thickness will).Described thickness ratio can be 1% to 50%, perhaps particularly, and 5% to 40%, perhaps more specifically, 10% to 25%.Usually, the gross thickness of this sheet material can be at the most or even above several millimeters.More specifically, the thickness of this sheet material (for example, accurate measurement) can be 1mil (25.4 microns (μ m)) to 500mils (1,2700 μ m), perhaps still more specifically, about 5mils (127 μ m) is to about 40mils (1016 μ m) and still more specifically, and about 5mils (127 μ m) is about 30mils (762 μ m) extremely.
Following example only be exemplary be not restriction of the present invention.
Embodiment
Embodiment 1
The duplicature of various cap rock compositions and membrane structure (sample 1 to 13 in the table 2) uses the described coextrusion method preparation according to Fig. 2.The concrete technological parameter of each sample is along with the thickness of each layer and total film thickness and change, and the process parameters range that relates to samples all in the table 2 provides in table 3.Should be appreciated that the process window that is used for extruding these films is not limited to listed those of table 3.The purpose of this experiment is to determine whether to exist " a kind of " condition, can prepare the film of these coextrusion under this condition, and promptly whether these films are extrudable.Table 3 only provides one group of condition that is used for these films of coextrusion.
This example has proved the disclosed suitability that is used for the goods of in-mold decoration (IMD) application.The film that is used for these application should meet three sub-technologies (sub-processes) of IMD: (a) extrudability-prepare the ability of film with the surface quality suitable with the graphic films (for example, Lexan 8010 films) of commercially available polishing by selected material; (b) formability-film the is pulled into ability of different geometries; (c) this film of pruning-clarity ground cutting and do not cause any breaking or the ability of layering.
Table 1 contains chemical descriptor and is used for the source of the resin of the listed membrane structure of table 2.
Figure BPA00001186546600071
1The Mw=weight average molecular weight
2PS standard specimen=record (GPC) by gel permeation chromatography
Table 2 has been estimated this sample aspect measuring in above 3 kinds of character: surface quality, and thermal formability, and prune.In order to measure surface quality, detect 10 sheets that are of a size of 12 inches of 12 inches x (30.5cm x 30.5cm) by three operators, determine in the longitudinal direction any defective (line, indenture, projection) greater than 2mm.For naked eyes, without any this defective just think " by ".Be not intended to test the optical quality of this film, but intention determines to show any gross imperfection of any problem that the film coextrusion produces.
In order to test formability, 12 inches samples of 12 inches x of this film are preheated to 140 ℃, vacuum forming on COMET Thermoformer then, wherein type instrument in Yangcheng is in 120 ℃, minimum curvature is that 5mm and maximum towing (maximum draw) are 10mm." qualified " of this test is, measures by naked eyes, do not exist in any wrinkle on this film in process, bleaches, and perhaps tears.(naked eyes do not comprise and are used to the optical device that amplifies that exception is the correcting lens that can use twenty-twenty vision required.)
The metal die head that use is complementary, the formpiston head part and the former head part (American Iron and Steel Institute " AISI " Type A2 steel) that comprise sclerosis are pruned the parts of described moulding, and the gap between described formpiston head part and the former head part is 10% of a sheet thickness; Wherein these parts are an angle of 90 degrees with respect to blade when impacting.The parts of pruning described thermoforming are a complete step in the IMD method.Sandwich construction with poor interlayer adhesion strength in the process of this step, be easy to come unstuck (delaminate).The qualified of this test is not have any visible break sign and any visible coming unstuck in the process of this step, and observability makes with the naked eye and measures.
Figure BPA00001186546600081
Figure BPA00001186546600091
Figure BPA00001186546600092
Table 2 causes following conclusion: the film of (1) coextrusion demonstrates the hardness of remarkable improvement, even 10% cap rock also has the hardness above H; (2) can improve pencil hardness though increase the thickness of cap rock, it makes this film become fragile, and this can find out (sample 4 though it demonstrates the pencil hardness of 4H, breaks, and therefore is not suitable for IMD) from pruning performance in the pruning process; (3) polyester in the basal layer makes that this film is that (100% PC has brought challenge for the coextrusion of cap rock to IMD close friend in the basal layer.)。Depth of cover 10% (sample 6) can not be extruded this film, and higher cap rock-basal layer than under can this film of coextrusion (sample 5), it is by pruning test, wherein it has caused coming unstuck between cap rock and the basal layer; (4) for example for the ease of coextrusion, according to the type of polyester, with the PC blend may be useful, for example, the ratio of blend is 0% to more than 20%, based on the gross weight of basal layer.Though 100%PCTG is extrudable as basal layer, PCCD and PC blend are made it possible to extrude.Therefore, if use PCCD, basal layer can comprise the PCCD of 20wt% to 90wt% so, perhaps particularly, and the PCCD of 30wt% to 80wt%, perhaps more specifically, the PCCD of 40wt% to 60wt%, surplus is PC.In addition, depth of cover can be 1% to 50%, perhaps particularly, and 5% to 40%, perhaps more specifically 10% to 30% and still more specifically, 15% to 25%.
Embodiment 2
The hardness and the scratch resistance of present embodiment explanation multilayer film.According to film listed in the table 4 and two samples of resin combination preparation.With with embodiment 1 in identical mode prepare these samples.Sample 14 is monofilm in essence, with it comprise into here relatively be by performance improvement that cap rock brought for outstanding.
Figure BPA00001186546600101
These two samples and three commercially available samples that are used for graphical application are contrasted: the polycarbonate membrane of 2 layers of coextrusion.This cap rock is the PC copolymer, and basal layer is PC (commercially available particularly from SABIC Innovative Plastics, Pittsfield, the Lexan ML 9735 of MA) (sample 17) (being called 1HD00, commercially available from SABIC Innovative Plastics); Individual layer Merlon (sample 18) Merlon (Lexan 8010, and is commercially available from SABIC Innovative Plastics); With the polycarbonate membrane (sample 19) that applies, it comprises that the curable silica dioxide coating (Lexan 8010 particularly) based on Merlon (is called HP92S, commercially available from SABIC Innovative Plastics), all is all commercially available from SABIC Innovative Plastics.Must point out that HP92S is the film that applies, it is not plastic.
According to the hardness of ASTM D3363-05 test all samples, i.e. pencil hardness.Two samples 15 and 16 pencil hardness are 2H all, and sample (17,18,19) has lower hardness: be respectively 1H, 2B, and HB.The hardness of sample 14 is 2B, and this has given prominence to the conspicuousness of cap rock.
Also use the scratch resistance of Erichsen Scratch Tester Type 413 specimen that meet ISO 1518.The power of 2 newton (N) and 4N is applied to the conical stylus that radius is 0.01 millimeter (mm), causes on this parts surface, producing indentation.Then measure the degree of indentation, and be recorded as bottom from indentation to the measured indentation height of sample surfaces with Dektak 6M talysurf.Once more, sample 15 and 16 has surpassed comparative sample.The sample 15 and 16 the scraping degree of depth are respectively 1.15 microns (μ m) and 1.25 μ m.The scraping degree of depth of comparative sample is respectively 1.4 μ m, 2.86 μ m and 2.95 μ m.The scraping degree of depth without any the sample (sample 14) of cap rock is 3.02 microns (μ m).
The data that produce in (table 5 and 7) are to produce under heavy load.Still in another case, use Nano Indenter XP, MTS Systems carries out little scraping experiment (underload), applies 0 to 50 little newton's (mN) normal load.Scraping speed is 50 microns per seconds (μ m/s).The Berkovich diamond indenter of use standard (having 10 nanometers (nm) sphere head) makes its blade be advanced through this material.Fig. 1 is a kind of explanation of this scraping, and the corresponding cut shape that records demonstrates the formation of scratch.Below record is the instantaneous depth (degree of depth in the process) of this shape of some place when load reaches 25mN.This has provided the measuring of softness (softness)/hardness of this material.Under the situation of having finished whole scraping (load reaches 50mN), some of cut are removed materials and have been restored, and result's degree of depth of swiping reduces.Measure the degree of depth and the width of cut again at above-mentioned identical some place.This is " the back degree of depth ".This has provided measure (" tolerance (forgiveness) ") of material recovery.
Figure BPA00001186546600111
Table 5 has emphasized that further the scratch resistance that is caused by described double-decker improves (sample 14 and 15/16 relatively).Not only performance is than sample 17 and 18 good for sample 15 and 16, and they also are suitable with respect to the comparative sample HP92S (sample 19) that applies.This is unforeseeable, and this is because people can expect originally that this coating had more patience owing to the crosslinked of them under this underload.
Except scratch resistance and hardness, mechanical strength also is the factor that IMD uses; For example, this film should withstand voltagely split and tear.Table 6 has write down in tearing of every millimeter of newton (N/mm) and has caused and spread intensity, and it uses ASTM D1004-03 respectively, and D1938-02 and ASTM D882 record.
Figure BPA00001186546600112
Can find out obviously that from table 6 scratch resistance of the improvement of seeing among the embodiment in front and hardness are not damaged the engineering properties of goods.
The scope that the application discloses comprises end points and is (for example, scope " about at the most 25wt%, perhaps more specifically, about 5wt% is to about 20wt% " comprises all intrinsic values of end points and " about 5wt% is to about 25wt%, " scope etc.) capable of being combined." combination " comprises blend, mixture, derivative, alloy, product etc.In addition, the application's term " first ", " second " etc. do not refer to any order, amount, perhaps importance, but be used for element is distinguished each other, term " one (a) " and " a kind of (an) " do not refer to quantitative limitation in this application, but refer to the object that has at least one indication.Modifier with the quantity coupling " pact " comprises described value, and has the pointed meaning of context (for example, comprising and the concrete relevant grade of errors of measuring of measuring method).Used suffix " (the s) " intention of the application comprises odd number and a plurality of term that it is modified simultaneously, comprises one or more this term (for example, colouring agent (s) comprises one or more colouring agents) thus.Alleged " a kind of embodiment " in whole specification, " another embodiment ", the meanings such as " embodiments " is meant that the concrete element described explicitly with this embodiment (for example, feature, structure, and/or characteristic) is included in the described at least a embodiment of the application, and can exists or can not be present in other embodiment.In addition, should be appreciated that described element can combination in any suitable manner in various embodiments.The used term " (methyl) acrylate " of the application comprises acrylate and methacrylate based group.Compound uses standard terminology to describe.For example, any valence link that is not interpreted as it by the position that any described group replaced by shown in key or hydrogen atom fill.(" ") is not used to represent the attachment point that replaces to the strigula between two letters or symbol.For example ,-CHO is attached by the carbon atom of carbonyl.
With the full content of all patents, patent application and other list of references quoted all by with reference to incorporating the application into.But,, have precedence over afoul with it term from the list of references of incorporating into from the application's term if when the term among the application conflicts on the contrary or mutually with the term of the list of references of incorporating into.
Though with reference to preferred embodiment having described the present invention, it should be appreciated by those skilled in the art that and to make various variations, and equivalent can replace its composition, and not depart from scope of the present invention.In addition, can make many versions,, and not depart from scope of the present invention so that concrete situation or material are adapted to instruction of the present invention.Therefore, expectation the invention is not restricted to conduct and carries out the disclosed specific embodiment of best mode of the present invention, and the present invention will comprise all embodiments in the scope that falls into claims.

Claims (13)

1. sheet material, it comprises:
The cap rock that contains acrylic polymer; With
Basal layer, described basal layer comprise present cycloaliphatic polyesters copolymer and optional aromatic polycarbonate, and wherein said present cycloaliphatic polyesters copolymer comprises alicyclic diol or acid or its combination of content greater than 10wt%, based on the gross weight of present cycloaliphatic polyesters copolymer;
Wherein said sheet material is thermoformable.
2. the sheet material of claim 1, wherein said cap rock is 1% to 50% of a gross thickness, described gross thickness is 5mil to 500mil.
3. claim 1 or 2 sheet material, wherein said basal layer comprise the blend of the Merlon of the present cycloaliphatic polyesters that contains 20wt% to 100wt% and surplus.
4. the sheet material of claim 3, wherein said blend comprises the present cycloaliphatic polyesters of 50wt% to 90wt%, surplus is a Merlon.
5. each sheet material among the claim 1-4, the pencil hardness of wherein said sheet material is greater than HB.
6. each sheet material among the claim 1-5, the tearing of wherein said sheet material cause intensity for more than or equal to 120N/mm.
7. each sheet material among the claim 1-6, the tearing of wherein said sheet material spread intensity and are higher than 5N/mm.
8. each sheet material among the claim 1-7, the tensile strength of wherein said sheet material is greater than 40MPa.
9. each sheet material among the claim 1-8, wherein said basal layer comprises 20wt% to 90wt%PCCD, surplus is an aromatic polycarbonate.
10. each sheet material among the claim 1-9, wherein said acrylic polymer is poly-(methyl) alkyl acrylate.
11. each sheet material among the claim 1-10, wherein said cap rock are poly-(methyl) methyl acrylates.
12. make the method for goods, it comprises:
Make acrylic polymer fusion in extruder;
Form the present cycloaliphatic polyesters copolymer of fusion in extruder, wherein said present cycloaliphatic polyesters copolymer comprises the present cycloaliphatic polyesters of content greater than 10wt%, based on the gross weight of present cycloaliphatic polyesters copolymer;
Described acrylic polymer of coextrusion and described present cycloaliphatic polyesters copolymer, thus sheet material formed, and wherein said present cycloaliphatic polyesters copolymer forms basal layer, and described acrylic polymer forms cap rock on described basal layer.
13. the method for claim 12 also comprises the described sheet material of thermoforming.
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US20090191403A1 (en) 2009-07-30
EP2237949A1 (en) 2010-10-13
TW200946337A (en) 2009-11-16
TWI396625B (en) 2013-05-21
CN102083623B (en) 2014-08-27
US20110189449A1 (en) 2011-08-04
EP2237949B1 (en) 2012-10-31
US7923100B2 (en) 2011-04-12

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